Yes
Doctor Who: The End of Time was released on DVD and Blu-Ray on March 2, 2010
Doctor Who Time Crash - 2007 TV is rated/received certificates of: UK:U (DVD release)
Doctor Who - 1963 The Time Warrior Part One 11-1 is rated/received certificates of: Australia:PG (DVD rating) Australia:G (video rating) UK:PG (DVD rating)
Doctor Who - 1963 The Time Warrior Part Four 11-4 is rated/received certificates of: Australia:PG (DVD rating) Australia:G (video rating) UK:PG (DVD rating)
Doctor Who - 1963 The Time Warrior Part Two 11-2 is rated/received certificates of: Australia:PG (DVD rating) Australia:G (video rating) UK:PG (DVD rating)
Doctor Who - 1963 The Time Warrior Part Three 11-3 is rated/received certificates of: Australia:PG (DVD rating) Australia:G (video rating) UK:PG (DVD rating)
From any retailer of DVD's or online. A wide selection of Hartnell DVD's are available ranging from An Unearthly Child to The War machines. More are being added next year (2012)
It is already out on DVD.
Doctor Who - 2005 The End of Time Part One is rated/received certificates of: Australia:PG UK:PG (DVD rating)
Doctor Who - 2005 The End of Time Part Two is rated/received certificates of: Australia:PG UK:PG (DVD rating)
Doctor Who - 1963 The War Machines Episode 3 3-44 is rated/received certificates of: Australia:G Australia:PG UK:PG (DVD rating)